Diphenylethers having herbicidal properties

ABSTRACT

1. A PROCESS FOR PRODUCING A DIPHENYLETHER HAVING THE GENERAL FORMULA:   Y-(3-X,Z-1,4-PHENYLENE)-O-(3-(R-O-)-1,4-PHENYLENE)-NO2   WHEREIN X REPRESENTS A HALOGEN ATOM OR A METHYL RADICAL IN THE 2-POSITION; Y REPRESENTS A HALOGEN ATOM OR AN ALKYL RADICAL HAVING UP TO 3 CARBON ATOMS IN THE 4-POSITION; Z REPRESENTS HYDROGEN OR HALOGEN IN THE 5- AND 6POSITIONS, WHEREIN BOTH THE 5- AND 6-POSITIONS MAY BE HYDROGEN, BUT ONLY ONE OF THE 5- OR 6-POSITIONS MAY BE HALOGEN; AND R REPRESENTS A SATURATED OR AN UNSATURATED HYDROCARBON HAVING UP TO 3 CARBON ATOMS, METHOXYETHYL OR AN ETHOXYETHYL RADICAL, WHICH COMPRISES REACTING IN THE PRESENCE OF AN ALKALI METHYL HYDROXIDE OR CARBONATE A 2,4-DIHALONITROBENZENE HAVING THE GENERAL FORMULA:   1-(O2N-),2,4-DI(HAL-)-BENZENE   WHEREIN HAL IS A HALOGEN ATOM, WITH A SUBSTITUTED PHENOL HAVING THE GENERAL FORMULA:   Y-(3-X,Z-1,4-PHENYLENE)-O-(4-(O2N-)-1,3-PHENYLENE)-O-   2-X,4-Y,Z-PHENOL WHEREIN THE MOLAR RATIO OF THE PHENOL TO THE 2,4-DIHALONITROBENZENE IS AT LEAST 2:1, AT A TEMPERATURE OF FROM 130* C. TO 160* C. TO PRODUCE A 2,4-BIS(SUBSTITUTED PHENOXY) NITRO BENZENE HAVING THE GENERAL FORMULA: 1-(O2N-),2,4-BIS((2-X,4-Y,Z-PHENYL)-O-)BENZENE THEN REACTING SAID 2,4-BIS(SUBSTITUTED PHENOXY) NITROBENZENE (IV) IN THE PRESENCE OF AN ALKALI METAL HYDROXIDE WITH AN ALCOHOL OF THE FORMULA ROH WHEREIN R IS AS DEFINED ABOVE AT A TEMPERATURE OF 20-100* C. TO PRODUCE SAID DIPHENYLETHER (I) AND A SUBSTITUTED PHENOL (III) AND THEREAFTER ISOLATING SAID DIPHENYLETHER (I).

United States Patent Ofice 3,849,503 DIPHENYLETHERS HAVING HERBICIDALPROPERTIES Itaru Shigehara, Kusatsu, Ryuyo Nishiyama, Kyoto, and RyoheiTakahashi, Kanichi Fujikawa, Tadaaki Toki, Hidetoshi Takagi, Rikuo Nasu,Isao Yokomichi, Furnio Kimura, and Shinzo Someya, Kusatsu, Japan,assignors to Ishihara Sangyo Kaisha Ltd., Nishiku, Osaka, Japan NoDrawing. Original application Oct. 14, 1970, Ser. No. 80,807. Dividedand this application Dec. 21, 1972, Ser. No. 317,155 Claims priority,application Japan, Oct. 14, 1969, 44/231,971; Apr. 22, 1970, 45/ 33,793;May 6, 1970, IS/37,902, 45/257,903; June 5, 1970, 45/47,929

Int. Cl. C07c 43/20 US. Cl. 260-613 R 6 Claims ABSTRACT OF THEDISCLOSURE Diphenylethers have been produced having the general formula:

I'i (LR wherein X represents a halogen atom or a methyl radical in the2-position; Y represents a halogen atom or an alkyl radical having up to3 carbons atoms in the 4-position; Z represents hydrogen or halogen inthe 5- and 6-positions, wherein both the 5- and 6-positions may behydrogen, but only one of the 5- or 6-positions may be halogen; and Rrepresents a saturated or an unsaturated hydrocarbon, having up to 3carbon atoms, or a methoxyethyl or ethoxyethyl radical. These compoundshave This is a division of application Ser. No. 80,807, filed Oct. 14,1970.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to novel diphenylethers, to herbicide products made from saiddiphenylethers, and further to new processes for producing the same.

Description of the prior art It has been known that variousdiphenylether compounds including 2,4 dichloro 4' nitrodiphenylether(TOK), 2,4,6 trichloro 4' nitrodiphenylether (MO) exhibit herbicidalproperties. Many other diphenylethers, however, having similar chemicalstructures as TOK and MO, have been found to have no herbicidal effects,and hence it has been presumed that the herbicidal properties are notdependent upon the diphenylether chemical formula alone. Althoughvarious studies have been made for been found to be useful asherbicides. diphenylethers having 4' nitrophenyl radicals, very few ofsuch compounds investigated to date have been found to exhibitherbicidal properties.

Summary of the invention Accordingly, it is one object of this inventionto provide a novel genus of diphenylethers. I

It is another object of this invention to provide a novel process forproducing said diphenylethers.

It is another object of this invention to provide a herbicide which willinhibit weed growth, yet which will not harm warm-blooded animals, suchas man or domestic animals, nor injure agricultural products.

3,849,503 Patented Nov. 19, 1974 A still further object of thisinvention is to .provide a herbicide which will inhibit weed growth andparticularly weed growth in wet lands, such as rice paddies and thelike, yet which is harmless to agricultural products.

These and other objects have now herein been attained by the discoverythat the substitution of a saturated or unsaturated alkoxy radical inthe 3'-position of the benzene ring of a 4-nitrophenyl radical willprovide a remarkably effective herbicidal compound. In particular, ithas been found that the novel diphenylethers of the following generalformula possess remarkable herbicidal properties:

X OR (I) wherein X represents a halogen atom or a methyl radical in2-position; Y represents a halogen atom or an alkyl radical having up to3 carbon atoms in 4-position; Z represents hydrogen or halogen in the 5-and 6-positions, wherein both the 5- and 6-positions may be hydrogen,but only one of the 5- or 6-positions may be halogen; and R represents asaturated or an unsaturated hydrocarbon, having up to 3 carbon atoms, ora methoxyethyl or ethoxyethyl radical.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Illustrative of some ofthe diphenylethers within the genus of formula (I) include 2,4 dichloro3' methoxy 4 nitrodiphenylether, 2,4 dichloro 3' ethoxy- 4'nitrodiphenylether, 2 chloro 4 methyl 3 methoxy 4 nitrodiphenylether, 2chloro 4 methyl 4- ethoxy 4 nitrodiphenylether, all of which have beenfound to possess remarkably good herbicidal properties. It has beenfound that if the other phenyl radical is 3- chlorophenyl, 3methylphenyl or 3,5 dimethylphenyl, such as 3 chloro 3 methoxy 4nitrodiphenylether, 3 chloro 3' ethoxy 4' nitrodiphenylether, 3 methyl3' methoxy 4 nitrodiphenylether, 3 methyl- 3 iso propoxy 4'nitrodiphenylether, 3,5 dimethyl 3' methoxy 4' nitrodiphenylether, 3,5dimethyl- 3 n propoxy 4 nitrodiphenylether, the substitution of the ORgroup at the 3'-position of the benzene ring in the 4-nitrophenylradical will result in decreased herbicidal effects. Moreover, it hasbeen found that the substitution of an --OR grouping in the 2-positionof the benzene ring in the 4-nitrophenyl radical, such as 2,4- dichloro2 methoxy 4' nitrodiphenylether, or the substitution of a NO group inthe 3'-position of the benzene ring in the 4'-nitrophenyl radical suchas 2,4- dichl'oro-3',4'-dinitrodiphenylether, will result in compoundshaving no herbicidal properties.

Furthermore, it has been found that diphenylethers having3'-(OR-substituted)-4-nitrophenyl radical having another substituentsuch as 2,4dichloro-3',6-dimethoxy- '-nitro diphenylether,2,4-dichloro-3-methoxy-4'-nitro-6'- chloro diphenylether,2-chloro-4-methyl-3',6'-dimethoxy- 4'-nitro diphenylether,2-methyl-4-chloro-3',6-dimethoxy- 4'-nitro diphenylether, 2,4dimethyl-3',6-dimethoxy-4'- nitro diphenylether,2,4,S-trichloro-3',6-dimethoxy-4'-nitro diphenylether, also exhibitlittle or no herbicidal properties.

In said diphenylethers having formula (I), if OR in 3'- position issubstituted by halogen, alkyl, alkylthio, alkylamino or fluoromethylradical, the advantages of herbicidal properties of the compound areless than those of the compound having the general formula (I).

In accordance with this invention, it has now been found that the noveldiphenylethers having the general formula TABLE II Amount of activeingredient (gJaere) Test plant Degree of growth (percent) TABLE1Continued Amount of active ingredient (gJeere) Degree of growth(percent) Barnyard grass 'IOK 000000000000000uooooooomooooooooooo 1 o000000000000OOOOOOOOOWOOOOOOOOOO 1 1 Represents the references.

Mono- False pimpernel Toothcup (Rotala in compari- -leaved weeds of longTABLE III Degree of growth control Amount of active ingredient (gJacre)Test plant EXPERIMENT 3 Tests for herbicidal effect on the paddy fieldweeds were conducted as follows: Pots of 1/30 m? were filled with 40soil and were supersaturated with water. Seed of Slender In Table III,the degree of growth control is stated 55 under the following standards:

son with untreated ones) to a depth of 3 cm. After the weeds wereemerged, anaqueous dispersion of each active ingredient of this inven-50 tion was sprayed onto the weeds. Fourteen days after said or Needlespikerush (Eleocharis aciculm'is ROEM et SCHULT) and seed of broadsteemed water-wort (Elatine triandra SCHK) choria (Monochoria vaginalisPRESL) (Lindernia pracumbens PHHJCOX) indica KOEHNE) were placed intorespective pots at a thickness of about 5 mm. Water was poured into eachpot treatment, each survival grass of said slender or needle spikerushand broad-leaved weeds was observed. The results are shown in Table III.

5: 100% growth suppression is found 4: About 90% growth suppression isfound 3: About 70% growth suppression is found 2: About growthsuppression is found 1: About 30% growth suppression is found Compoundnumber:

l Represents the ecmpcunds which are outside scope of invention.

EXPERIMENT 2 Tests for selective growth controlling effect between riceand barnyard grass were made by the following method.

Pots of 1/ m? were filled with soil and were super-' saturated withwater.

A specific amount of germinated rice seed and air-dried barnyard grassseed was sown into each pot and covered with soil. The germinated riceseed used in this test was prepared by soaking dried rice seed in Waterfor germination, and, thereafter, selecting those seeds of the samegerminated condition.

When the barnyard grass was grown to 1.5 leaves, water was poured intoeach pot to a depth of 4 cm. and an aqueous dispersion of one of theactive ingredients of this invention was poured into the pot. Eighteendays after the treatment, the surviving rice plants and barnyard grasswas taken up and weighed and air-dried.

8 EXPERIMENT 5 Dwee gmwth cmtml Tests for herbicidal effect on theup-land weeds in the Amount of active ingredient (gJacre) fieldcondition were conducted as follows:

TABLE IIICntinued m m mma fia a .1 M. t. S O W 8h 6 wnmum mt u w i n e a.ew wmmmww E umw mmmm w .m m m a em u m [Ln nao S 6k mai a w mmnmdmmm wt n U a%% H t. n O S w h m m 6 Sm n S2 t m u a U M d m e o e u a w k p iaw m r n n s e e a w m m m M H c v m m m a m w m n w .m ww dvw m m 0 ,etalr e 0 6wb fi wmmvk M e t & an T V b m ufaam w.wm w W .w o m n a o oefl.ws r D a mmm wwmhw a 7 I a dmom fi a a m wefi c g gap dA M mWnMw amad b n 6 en t W 1 o rs maes a e m I60t. e

LG kdvomwmcm m m 5 m w. P 5553544554554554444 d4 Test plant P 555D-O55555555555555 05 Broad-leaved weeds Degree of chem- 1,e00, s00, icalacre gJacre injury 22 29 days days days crabgrass Wire grass Amount ofactive ingredients 1 600, 800, 1,600, 800, g./acre glaere g./acreg./aere g./

EXPERIMENT 6 Comparative tests for the residual effect on paddy fieldwere measured as follows: Pots of m? were filled with soil and water waspoured to a depth of 3 cm. A specific TABLE VI Amount Degree of growth,percent of active ingredient 3 (g./acre) days days number:

after treatment, a specified amount of germinated barnyard grass wereput in the depth of about 5 cm. Fourteen days after the treatment, thesurviving barnyard grass was taken up, air dried and weighed. The degreeof growth was calculated as in Experiment 1. The results are shown ining to the sowing. The germinated barnyard-grass seeds were prepared bysoaking dried seeds.

concentration of aqueous dispersion of each ingredient was sprayed ontothe soil. After a specified number of days Table VI wherein Daysrepresents days after the spray- =Broad leaved weeds. EXPERIMENT 4 Testsfor herbicidal effect on the upland weeds in the 25 green house wereconducted as follows: Each pot of 1/ 30 Compound m? was filled with soilcontaining a general upland weed seed of Water foxtail (Alopecurusaequalis SOBOL var.

IGeiflleral d 88 S Pea pl l x) Compound number.

TABLE IV Degree of growth control Amount of active ingredients RiceRadish 1 Represents the references.

NoTE.O=Slender or needle spikerush; P

The seeds of rice, radish and pea were sown in the pots and were coveredwith soil to a depth of about 1 cm.

In the Table IV, the degree of growth control is stated using thefollowing standards:

amurensis OHWI) Large crabgrass (Digitaria adscendens HENR) Wavybittercress (Cardamine flexuosa WITH) and maintained in uplandcondition.

ous dispersion of each ingredient was sprayed onto the soil. Afterfourteen days from said spraying, the growth condition of each of therice, radish, pea and general upland weeds was observed. The results areshown in Table Three days after sowing, the specific amount of an aque-2: Necrosis of leaves is found but disappears later 1: Same conditionwith untreated case 5: Complete growth suppression is found 4:Remarkable growth suppression is found 3: Clear growth suppression isfound Compound number escre gSS ma qmmmmm cww m evmm n G g n H r r O mer l fmd n .1 Oa wg t p h 4L n r W O a d S01 5.1 g g n so w o wd e000000000 7 B wm W T im f m mn 000 O00 000 m h :1 MW M Sd W 000 000 00 t.1 5

4 68 408 Q68 B sp ank 2 1 2 1 2 1 P m mmhw ma E .5 H. m

trd: r ue n a mu n a Sf t. n

m m m mm md ei u aemnm .w an

O n I W 1 O Sh T M dfidao owa 5 O 5 O 5 6 G 7 5D43H4345J034H34Av4434334544 .14 0434 4 4 5 calculated as inExperiment 1. Days represents days 9 after the spraying on the sownsoil. The germinated barnyard-grass are same with that of Experiment 6.

As the results of said experiments, the novel compounds of thisinvention have excellent herbicidal properties and can be used in a widevariety of environments such as paddy fields, uplands, orchards, turves,woodlands, loadside, bank, railroad, play ground, lake-side, watersupply, brook, etc.

The herbicides of this invention have the following variouscharacteristic advantages as compared with conventional TOK, MO, etc:

(1) They have remarkably good herbicidal properties against weeds inpaddy fields, such as barnyard grass, etc. They can suppress said weedswith smaller amounts of ingredient. (Experiment 1.)

(2) The activity of the ingredients is high, even when diluted, so thatthey can be applied in low concentration. (Experiment 1).

(3) They have remarkably good selective growth control properties forherbicide barnyard grass (belonging to the same genus) without injury torice. (Experiment 2.)

(4) They have remarkably good growth suppressing properties againstslender or needle spi-kerush and broadleaved weeds such as Long stemmedwater-wort, Monochoria, False Pimpernel, Toothcup, which are grown onwet or semi-wet ground. (Experiment 3.)

(5) They have growth suppressing effect against Water foxtail, Largecrab-grass, Wavy bittercress, Wire grass, Ladys-thumb, Common purslane,however, they will not suppress the growth of rice, radish, pea orpeanuts. (Experiments 4 and 5.)

(6) They exhibit remarkably good durability of growth suppressingeffect, i.e., residual effect against weeds on wet ground as well as dryground. (Experiments 6 and 7.)

The quantity of herbicide of this invention required depends upon theweather, soil, form of preparation of agent, season, method ofapplication and weeds. Usually l00-4,000 g. per acre and preferably2002,400 g. per acre is effective. The herbicidal compounds of thisinvention can be applied in the form of an aqueous dispersion, a dust,at granule, a wettable powder, a water miscible solution or an emulsionwith auxiliary agents such as diluent, solvent, emulsifier and spreader.The herbicidal compounds of this invention may be used together withother herbicidal compounds, insecticides, fungicides, fertilizers orsoils. Sometimes, more effective results are obtained when applied incombination with such other materials.

The novel diphenylether of this invention may be synthesized by reactingan alkali metal salt of substituted phenol withZ-(OR-substituted)-4-halonitrobenzene. However, it is difficult toobtain high yields of the subject compound by said conventionalprocesses, because a relatively large quantity of an isomer by-productis produced.

It has been discovered, and is another feature of this invention, thatdiphenylethers can be synthesized in high yields economically byreacting 2,4-dihalonitrobenzene having the general formula:

Hal (I (wherein Hal is halogen atom) and a substituted phenol having thegeneral formula:

to produce a 2,4-bis-(substituted phenoxy)nitrobenzene having thegeneral formula:

Z (IV) This product is then reacted with a corresponding alcohol (ROH),R is corresponding to R defined in the formula (I), to produce the novelcompound having general formula (I) and the substituted phenol havingthe general formula of (III) and the former product is isolated. A highyield of the novel diphenylether is easily obtained using this method.The bis-( substituted phenoxy) nitrobenzene (IV) is obtained preferablyby the reaction of 1 mol of (II) and more than 2 mols of (III). Goodresults are obtained when the reaction occurs in the liquid phase and ina basic condition while heating. It is not always required to use asolvent, but it is possible to shorten the reaction time and obtain amore uniform reaction by using a suitable solvent.

The solvent should be inactive to the raw materials and alkali material.Suitable solvents include dioxane, isophorone, dimethylsulfoxide,dimethylacetoamide, and dimethylformamide as suitable ones.

In order to render the reaction media basic, an alkali metal hydroxideor carbonate may be added; such as, sodium hydroxide, potassiumhydroxide or sodium carbonate. If desired, a solution of the alkali saltof substituted phenol of (III) can be used to render the reaction basic.

The reaction temperature for producing (IV) should be above C., andpreferably between 160 C. If the reaction temperature is too low, thespeed of the reaction will be too slow. On the other hand, if thereaction temperature is too high, the resulting product may be coloredand undesirable side reactions may occur.

The first reaction is usually completed in about 3-6 hours and providesbis-(substituted phenoxy)nitrobenzene of (IV) in high yield. Thisproduct can be used in the second reaction without purification orconcentration, but it is also possible to use a purifiedbis-(substituted phenoxy)nitrobenzene.

The second reaction to produce 3'-(OR substituted)-4'-nitrodiphenylether from IV and ROH is also carried out in a basiccondition while heating. It is unnecessary to add a solvent, except ROH,however, if desired another organic solvent can be added.

The alkali used in the second reaction may be the same as that used inthe first reaction, or an alkolate pro duced by reacting ROH and analkali can be used for this purpose. The temperature of the secondreaction will depend upon the particular raw materials and theparticular solvent and is usually 20-100 C.

The second reaction is usually completed within 2-4 hours. The resultingproduct is cooled and put into water to separate the solid product andthen is purified to obtain a high yield of 3-(OR-substituted)-4'-nitrodiphenylether. The substituted phenol (III)containing said resulting solution may be recovered and used for thefirst reaction.

The following is illustrative of the process for producing the noveldiphenylethers of this invention.

1 1 EXAMPLE 1 810 grams (5 mol) of 2,4-dichlorophenol was placed into a2 liter, four necked flask equipped with a stirrer, funnel and refluxcondenser. The flask was heated to 120 125 C. in an oil bath. 322 grams(4.8 mol) of potassium hydroxide was added to the flask and distilled,the resulting water in vacuum. The flask was then heated to 140 C. and384 grams (2 mol) of 2,4-dichloronitrobenzene was added dropwise to themixture over a period of thirty minutes. The reaction mixture was thenheated to 140- 150 C. and maintained at this temperature for 4 hours.After the completion of the reaction was confirmed by gaschromatography,the oil bath was removed and the temperature was lowered to 9095 C. Onethousand ml. of dioxane was added to the flask and stirred after which amixture of 200 ml. of methyl alcohol, and 150 grams of potassiumhydroxide (2.3 mols) was also added. The temperature was maintained at55 C.i5 C. for two hours. After completion of the reaction was confirmedby gas-chromatography, the contents of the flask were cooled to 30 C.and was placed into six liters of water while being subjected to severestirring to separate a yellowish solid. The solid was filtered andwashed in six liters of water, and refiltered and washed with one literof ethyl alcohol. The solid filtrate was dried to obtain 622 grams ofsolid 2,4-dichloro-3-methoxy-4'-nitrodiphenylether (m.p. 1l2-1l4 C.).The yield of the product was 99%. In said process, 460 grams of2,4-dichlorophenol was recovered by adding hydrochloride to the filteredsolution. (Recovery was 95%.) Seven parts of 2,4-dichloro-3'-methoxy-4-nitrodiphenylether, 88 parts of bentonite, 5 parts of sodium ligninsulfonate were mixed and granulated with a small amount of water toobtain a herbicide preparation. Ten kg./acre of the herbicidepreparation was scattered over a paddy field and it was observed thatall weeds were suppressed.

EXAMPLE 2 384 g. of 2,4-dichloronitrobenzene, 810 g. of2,4-dichlorophenol and 322 g. of 85% of potassium hydroxide were reactedby the method according to Example I, and 200 ml. of ethyl alcohol, 150g. of potassium hydroxide and 100 ml. of dioxane were added and reactedto obtain 635 g. of 2,4-dichloro-3'-ethoxy-4-nitrodiphenylether (m.p.102104 C.). The yield of this product was 97%. 15 parts of2,4-dichloro-3-ethoxy-4'-nitrodiphenylether, 15 parts of polyoxyethylenestearate, 35 parts of isophorone and 35 parts of dioxane were uniformlymixed and dis solved to form a herbicide preparation (water misciblesolution). By spraying 8 kg./acre of this herbicide preparation over adry field, it was observed that all of the weeds were suppressed.

EXAMPLE 3 4.8 g. of 2,4-difluoronitrobenzene, 15.0 g. of 2,4,6-trichlorophenol. 4.7 g. of 85% potassium hydroxide and 30 ml. ofdimethylsulfoxide as solvent, were reacted by the method of Example 1.45 ml. of dioxane, 8.0 ml. of methyl alcohol and 3.0 g. of potassiumhydroxide were added and reacted to obtain 9.0 g. of 2,4,6-trichloro-3-methoxy-4-nitrodiphenylether (mp. 138140 C.). The yield of the productwas 85%.

EXAMPLE 4 77 g. of 2,4-dichloronitrobenzene, 162 g. of 2,4-dichlrophenoland 65 g. of 85% KOH were reacted by the method of Example 1, exceptthat a 1 liter, four-necked flask was used. 50 g. of methyl cellosolve,35 g. of KOH and 200 ml. of dioxane were added to the flask and reactedto obtain 130 g. of 2,4-dichloro-3-methoxyethoxy-4'-nitrodiphenylether(mp. 6263 C.). The yield of the product was 91%.

EXAMPLE 77 g. of 2,4-dichloronitrobenzene, 143 g. of 22-chloro-4-methylphenol and 65 g. of KOH were reacted by the method of Example 1,except that a 1 liter, four-necked flask was used. 2-propnyl alcohol, 35g. of KOH and 200 ml. of benzene were added to the flask and reacted toobtain g. of 2-chloro-4-methyl-3'(2-propenyloxy)-4'- nitrodiphenylether(m.p. 57-59 C.). The yield of the product was 92%.

EXAMPLE 6 40 parts of 2-ehloro-4-methyl-3'-ethoxy-4'-nitrodiphenylether, 55 parts of kaolin, 5 parts of sodium alkylbenzenesulfonate were mixed and powdered to form a herbicide preparation. 3kg./acre were sprayed on the wilds, and it was observed that all weedswere suppressed.

Having now fully described the invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of theinvention.

Accordingly, what is claimed and intended to be covered by letterspatent is:

1. A process for producing a diphenylether having the general formula:

wherein X represents a halogen atom or a methyl radical in the2-position; Y represents a halogen atom or an alkyl radical having up to3 carbon atoms in the 4-position; Z represents hydrogen or halogen inthe 5- and 6- positions, wherein both the 5- and 6-positions may behydrogen, but only one of the 5- or 6-positions may be halogen; and Rrepresents a saturated or an unsaturated hydrocarbon having up to 3carbon atoms, methoxyethyl or an ethoxyethyl radical, which comprisesreacting in the presence of an alkali metal hydroxide or carbonate a2,4-dihalonitrobenzene having the general formula:

HaIQAQOZ l lal (II) wherein Hal is a halogen atom, with a substitutedphenol having the general formula:

wherein the molar ratio of the phenol to the 2,4-dihalonitrobenzene isat least 2:1, at a temperature of from C. to C. to produce a2,4-bis(substituted phenoxy) nitro benzene having the general formula:

then reacting said 2,4-bis(substituted phenoxy) nitrobenzene (IV) in thepresence of an alkali metal hydroxide with an alcohol of the formula ROHwherein R is as defined above at a temperature of 20l00 C. to producesaid diphenylether (I) and a substituted phenol (III) and thereafterisolating said diphenylether (I).

2. The process of claim 1, wherein the first reaction and the secondreaction are each conducted in the presence of an organic solvent.

3. The process of claim 1, wherein the substituted phenol (III) obtainedby the second step reaction is recovered and reused in the first stepreaction.

the second reaction are each conducted in the presence of an alkalimetal hydroxide.

4. The process of claim 1, wherein the first reaction and 5. The processof claim 1, wherein the first and second reactions are conducted in thepresence of an organic solvent selected from the group consisting ofdioxane, isophorone, dimethylsulfoxide, dimethylacetoamide anddimethylformamide.

6. The process of claim 4, wherein the alkaline metal 10 hydroxide ispotassium hydroxide.

References Cited UNITED STATES PATENTS HOWARD T. MARS, Primary ExaminerN. CHAN, Assistant Examiner US. Cl. X.R. 71-124

1. A PROCESS FOR PRODUCING A DIPHENYLETHER HAVING THE GENERAL FORMULA: